US7148351B2 - Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems - Google Patents
Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems Download PDFInfo
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- US7148351B2 US7148351B2 US10/658,715 US65871503A US7148351B2 US 7148351 B2 US7148351 B2 US 7148351B2 US 65871503 A US65871503 A US 65871503A US 7148351 B2 US7148351 B2 US 7148351B2
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- United States
- Prior art keywords
- salts
- polymer
- tagged treatment
- acid
- polymers
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title abstract description 164
- 239000008235 industrial water Substances 0.000 title abstract description 43
- 150000003839 salts Chemical group 0.000 claims description 126
- -1 vinylbenzyloxy Chemical group 0.000 claims description 21
- 125000005336 allyloxy group Chemical group 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000002455 scale inhibitor Substances 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical class C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 238000000034 method Methods 0.000 description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 22
- 239000000700 radioactive tracer Substances 0.000 description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical class CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 12
- 239000003139 biocide Substances 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 10
- 239000011976 maleic acid Substances 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical class C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003115 biocidal effect Effects 0.000 description 9
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 9
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002202 Polyethylene glycol Chemical class 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920001223 polyethylene glycol Chemical class 0.000 description 7
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical class FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical class C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011970 polystyrene sulfonate Substances 0.000 description 6
- 229960002796 polystyrene sulfonate Drugs 0.000 description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 5
- RSNDTPFSMDVWCS-UHFFFAOYSA-N 2-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCC(=C)C(N)=O RSNDTPFSMDVWCS-UHFFFAOYSA-N 0.000 description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 5
- FDRMJKDXTZDBHQ-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;methyl hydrogen sulfate Chemical group COS([O-])(=O)=O.C[NH+](C)CCOC(=O)C(C)=C FDRMJKDXTZDBHQ-UHFFFAOYSA-N 0.000 description 5
- RFPLNIBCLGFBKV-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;methyl hydrogen sulfate Chemical group COS([O-])(=O)=O.C[NH+](C)CCOC(=O)C=C RFPLNIBCLGFBKV-UHFFFAOYSA-N 0.000 description 5
- YDJFNSJFJXJHBG-UHFFFAOYSA-N 2-carbamoylprop-2-ene-1-sulfonic acid Chemical compound NC(=O)C(=C)CS(O)(=O)=O YDJFNSJFJXJHBG-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 5
- RZVJZTAYJDXIDT-UHFFFAOYSA-N 3-carbamoylbut-3-ene-1-sulfonic acid Chemical compound NC(=O)C(=C)CCS(O)(=O)=O RZVJZTAYJDXIDT-UHFFFAOYSA-N 0.000 description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 5
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 5
- ZTUMLBMROBHIIH-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group ClCC1=CC=CC=C1.CN(C)CCOC(=O)C(C)=C ZTUMLBMROBHIIH-UHFFFAOYSA-N 0.000 description 5
- CEJFYGPXPSZIID-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl prop-2-enoate Chemical group ClCC1=CC=CC=C1.CN(C)CCOC(=O)C=C CEJFYGPXPSZIID-UHFFFAOYSA-N 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- GJIDOLBZYSCZRX-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical class OCOC(=O)C=C GJIDOLBZYSCZRX-UHFFFAOYSA-N 0.000 description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 5
- XALORNQYADLLCH-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide;methyl hydrogen sulfate Chemical group COS(O)(=O)=O.CN(C)CCNC(=O)C=C XALORNQYADLLCH-UHFFFAOYSA-N 0.000 description 5
- PHIAIMNBQOYUSA-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-2-methylprop-2-enamide;methyl hydrogen sulfate Chemical group COS(O)(=O)=O.CN(C)CCCNC(=O)C(C)=C PHIAIMNBQOYUSA-UHFFFAOYSA-N 0.000 description 5
- PMPYZXFIZYUAEN-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide;methyl hydrogen sulfate Chemical group COS(O)(=O)=O.CN(C)CCCNC(=O)C=C PMPYZXFIZYUAEN-UHFFFAOYSA-N 0.000 description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical group C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 5
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical class [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 5
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical class [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 5
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 5
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- 125000003277 amino group Chemical group 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000006085 branching agent Substances 0.000 description 4
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- BFKXHILYGIQGCB-UHFFFAOYSA-N 52083-08-6 Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3O BFKXHILYGIQGCB-UHFFFAOYSA-N 0.000 description 1
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- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BHLTXMYFQGRAOJ-UHFFFAOYSA-N C=CC.CC(=O)C1=CC=CC=C1 Chemical compound C=CC.CC(=O)C1=CC=CC=C1 BHLTXMYFQGRAOJ-UHFFFAOYSA-N 0.000 description 1
- UBSQRPCSMCQVAT-UHFFFAOYSA-N C=CC.CCC1=CC=CC=C1 Chemical compound C=CC.CCC1=CC=CC=C1 UBSQRPCSMCQVAT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000012625 in-situ measurement Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- ILCQQHAOOOVHQJ-UHFFFAOYSA-N n-ethenylprop-2-enamide Chemical compound C=CNC(=O)C=C ILCQQHAOOOVHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000009928 pasteurization Methods 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 235000013594 poultry meat Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Definitions
- This invention relates to fluorescent monomers. In another aspect, this invention relates to tagged treatment polymers that contain these fluorescent monomers. In a further aspect, this invention relates to the use of tagged treatment polymers containing fluorescent monomer(s) therein in industrial water systems.
- monitoring is meant herein any type of tracing or tracking to determine the location or route of the polymers, and any type of determination of the concentration or amount of the polymer at any given site, including singular or intermittent or continuous monitoring.
- monitoring it may be desirable to monitor water treatment polymers in water systems, or to monitor polymers that may be present in waste fluids before disposal, or to monitor the polymer used in fluids for down-hole oil well applications, or to monitor polymers that may be present in fluids used to wash a manufactured product.
- the purpose of such monitoring may be to trace or track or determine the level of the polymer itself, or to trace or track or determine the level of some substance in association with the polymer, or to determine some property of the polymer or substance in association with the polymer, for instance its leachability.
- the concentration of the treatment polymer in the water system is the important factor so that the treatment polymer performs the desired function with good efficiency.
- a treatment polymer added to a cooling water system can be consumed by many causes. With consumption, the amount of the treatment polymer dissolved in the cooling water does not remain the same as the amount added to the cooling water. Therefore, it is important for the optimum operation of an industrial water system that practical methods are known to determine the concentration of treatment polymers in the water of the industrial water system.
- the amount of the treatment polymer added to the water in an industrial water system can be measured using various analytical methods.
- the use of an inert fluorescent tracer or mass balance measurement method as described in U.S. Pat. Nos. 4,783,314; 4,992,380; and 5,171,450, hereby incorporated by reference; to perform this analysis is known in the art.
- an inert fluorescent tracer is added to an industrial water system, with the amount of inert fluorescent tracer added being proportional to the amount of the treatment polymer added.
- the amount of the inert fluorescent tracer can be determined by using a calibration curve to relate the amount of fluorescent signal detected to the amount of the inert fluorescent tracer present. Because the inert fluorescent tracer and the treatment polymer are added to the industrial water system in known proportions, by knowing the amount of inert fluorescent tracer present it also means that the amount of treatment polymer present is known.
- the inert fluorescent tracer method can be conducted on-line and in real time so that any changes in the amount of treatment polymer being added to the system can be made immediately.
- Certain tagged treatment polymers are known, see U.S. Pat. No. 5,986,030, and U.S. patent application Ser. No. 09/465,146, filed Dec. 16, 1999, now pending, hereby incorporated by reference.
- a fluorometer can be used to measure the fluorescent signal of the tagged treatment polymer and determine the concentration of tagged treatment polymer currently present in the industrial water system from that information.
- the first aspect of the instant claimed invention is a fluorescent monomer selected from the group consisting of compounds of the formulae:
- the second aspect of the instant claimed invention is a tagged treatment polymer selected from the group consisting of: G a Q j W t (1)
- the third aspect of the instant claimed invention is a process for the inhibition of scale formation in an industrial water system which comprises introducing into said industrial water system a tagged treatment polymer selected from the group consisting of: G a Q j W t (1)
- the fourth aspect of the instant claimed invention is a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
- a tagged treatment polymer selected from the group consisting of: G a Q j W t (1)
- the fifth aspect of the instant claimed invention is a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
- anionic counter ion refers to an organic or inorganic ion that bears a negative charge to counterbalance the positive charge present on the monomer. Examples include, but are not limited to chloride, sulfate, acetate, methylsulfate, hydroxide and bromide; “aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon atom; “substituted aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon of an organic molecule which may bear functional groups such as hydroxyl, carboxyl, etc.; “1,2-diamino-substituted aromatic compound” refers to aromatic diamines in which the two amino groups are attached to two adjacent carbons of an aromatic compound; “diamines” refers to an organic molecule which bears two amino groups anywhere in the molecule; “Aldrich” refers to Aldrich Chemical Company, P.O.
- alkyl refers to a fully saturated hydrocarbon moiety with from 1 to 10 carbon atoms
- dialkylamino refers to a moiety of the formula R 21 —N—R 22 , where R 21 and R 22 are alkyl
- alkoxy refers to a moiety of the formula RO—, where R is alkyl
- alkylamidoalkyl refers to a moiety of the formula R—C(O)NH—R 1 —, where R and R 1 are alkyl
- alkylamino refers to a moiety of the formula R—NH—, where R is alkyl
- alkoxylalkyl refers to a moiety of the formula R—O—R 1 , where R and R 1 are alkyl
- aryl refers to a moiety of the formula Ar—, where Ar is
- Cross-Linking Agent refers to an ethylenically unsaturated monomer either containing at least two sites of ethylenic unsaturation or containing one site of ethylenic unsaturation and one site of a reactive group such as an epoxide or an aldehyde.
- a Cross-Linking Agent is added to branch or increase the molecular weight of the tagged treatment polymer of this invention.
- Cross-Linking Agents include N,N-methylenebisacrylamide, N,N-methylenebismethacrylamide, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, N-vinyl acrylamide, divinyl benzene, triallyl ammonium salts, N-methyl allylacrylamide, glycidyl acrylate, acrolein, methylolacrylamide, glyoxal, epichlorohydrin, and the like.
- the crosslinker is added at from about 0.0001 to about 10, preferably from about 0.0001 to about 0.2 weight percent based on the weight of the polymer;
- Branching Agent refers to a “Cross-Linking Agent” that is administered at a low level (less than 0.05 weight percent based on the weight of the polymer). It is understood that Branching Agents are added to form “branches” not cross-links; and
- HLB refers to a hydrophilic-lipophilic balance number
- the present invention is based upon the discovery of a group of fluorescent monomers which are useful in the preparation of tagged treatment polymers containing same, with said tagged treatment polymers in turn being able to provide a means for achieving better monitoring in industrial water systems.
- the first aspect of the instant claimed invention is a fluorescent monomer selected from the group consisting of compounds of the formulae:
- Monomers of formula (Purple) can be synthesized by using two different synthetic routes. Materials required for these syntheses are commercially available and can be obtained from Aldrich.
- the first synthetic route involves initially reacting a sulfonic or carboxylic-substituted naphthalic anhydride with 2,3-diamino-phenol. This compound is then further reacted with an allyl or vinylbenzyl halide to yield Monomer (Purple) where R 3 is allyloxy or vinylbenzyloxy and R 4 is carboxylic or sulfonic acid.
- the second synthetic route involves reacting 4-hydroxy-1,8-naphthalic anhydride with a carboxylic or sulfonic-substituted-diamino aromatic compound. This compound is then further reacted with an allyl or vinylbenzyl halide to yield Monomer (Purple) where R 3 is carboxylic or sulfonic acid and R 4 is allyloxy or vinylbenzyloxy.
- “Tagging” the polymer through the use of the fluorescent monomers of this invention is achieved by synthesizing the polymer in the presence of the fluorescent monomer.
- the selected monomer can be used to synthesize tagged treatment polymers of formula: G a Q j W t (1)
- tagged treatment polymers can be synthesized by following the procedure for conventional free radical polymerization in an aqueous medium. They can be made by water-in-oil polymerization methods or dispersion polymerization methods or solution polymerization methods. For those tagged treatment polymers containing a sulfomethylated or sulfoethylated acrylamide, the polymers are first created with an acrylamide moiety, and then the acrylamide groups are sulfomethylated using a suitable “sulfo” reagent such as formaldehyde and sodium metabisulfite.
- a suitable “sulfo” reagent such as formaldehyde and sodium metabisulfite.
- a general procedure for the manufacture of water-in-oil emulsion tagged treatment polymers is provided to illustrate the preparation of these tagged treatment polymers using fluorescent monomers.
- the types and quantities of specific components in the formula will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
- An aqueous phase is prepared by mixing together in water one or more water soluble monomers, and different polymerization additives such as inorganic salts, chelants, pH buffers, Chain Transfer Agents and Branching or Cross-Linking Agents.
- a monomer of formula Monomer (Purple) is included in the aqueous phase at the desired level.
- An organic phase is prepared by mixing together an inert hydrocarbon liquid with one or more oil soluble surfactants.
- the surfactant mixture should have a low HLB, to ensure the formation of an oil continuous emulsion.
- Appropriate surfactants for water-in-oil emulsion polymerizations, which are commercially available, are compiled in the North American Edition of McCutcheon's Emulsifiers & Detergents .
- the oil phase may need to be heated to ensure the formation of a homogeneous oil solution.
- the oil phase is charged into a reactor equipped with a mixer, a thermocouple, a nitrogen purge tube, and a condenser. Adding the aqueous phase to the reactor containing the oil phase with vigorous stirring forms an emulsion. The resulting emulsion is heated to the desired temperature, purged with nitrogen, and a free-radical initiator is added. The reaction mixture is stirred for several hours under a nitrogen atmosphere at the desired temperature. Upon completion of the reaction, the water-in-oil emulsion polymer is cooled to room temperature, where any desired post-polymerization additives, such as antioxidants, or a high HLB surfactant (as described in U.S. Pat. No. 3,734,873) may be added.
- any desired post-polymerization additives such as antioxidants, or a high HLB surfactant (as described in U.S. Pat. No. 3,734,873) may be added.
- the resulting emulsion polymer is a free-flowing liquid.
- An aqueous solution of the water-in-oil emulsion polymer can be generated by adding a desired amount of the emulsion polymer to water with vigorous mixing in the presence of a high-HLB surfactant (as described in U.S. Pat. No. 3,734,873).
- a general procedure for the manufacture of dispersion tagged treatment polymers is provided in the following text in order to illustrate the preparation of dispersion tagged treatment polymers comprising the fluorescent monomers described herein.
- the types and quantities of specific components in the formula will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
- aqueous solution containing one or more inorganic salts, one or more water-soluble monomers, any polymerization additives such as chelants, pH buffers, Chain Transfer Agents, Branching or Cross-Linking Agents and a water-soluble stabilizer polymer is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen purging tube, and a water condenser.
- the monomer solution is mixed vigorously, heated to the desired temperature, and then a water-soluble initiator is added.
- the solution is purged with nitrogen while maintaining temperature and mixing for several hours. After this time, the products are cooled to room temperature, and any post-polymerization additives are charged to the reactor.
- Water continuous dispersions of water-soluble polymers are free flowing liquids with product viscosities generally 100–10,000 cP, measured at low shear.
- a monomer of formula Monomer (Purple) is included in the reaction mixture at the desired level.
- a general procedure for the manufacture of solution polymers is provided to illustrate the preparation of the solution tagged treatment polymers comprising the fluorescent monomers described herein.
- One typical process is described as follows: One or more monomers are added to a vessel followed by neutralization with a suitable base. The fluorescent monomer can then be added to this monomer solution after neutralization or alternatively, to the reaction vessel. A determined amount of water is then added to the reaction vessel, which is then heated and purged. Polymerization catalysts may also be added to the vessel initially or fed in gradually during the course of the reaction. Water soluble polymerization initiators such as any azo or redox initiator or combination thereof are added along with the monomer solution to the reaction mixture in separate feeds over the same amount of time, usually 2 to 6 hours. The reaction temperature is maintained at about 60–70° C. Additional initiator may be used after addition is complete to reduce residual monomer levels.
- the amount of fluorescent monomer that is used should be an amount sufficient to allow the tagged treatment polymer to be detected in the aqueous environment that it is used.
- the minimum amount of fluorescent moiety that can be used is that amount which gives a signal-to-noise ratio (S/N) of 3 at the desired tagged treatment polymer dosage.
- S/N signal-to-noise ratio
- the signal-to-noise ratio is that value where the magnitude of the transduced signal (including but not limited to electronic and optical signals) due to the presence of a target analytic in a measurement device is greater than or equal to a level three (3) times the magnitude of a transduced signal where the analyte (species) of interest is not present in the measurement device.
- the amount of fluorescent monomer in the tagged treatment polymers is in the range of from about 0.001 mole percent to about 10 mole percent, preferably from about 0.01 mole percent to about 0.4 mole percent, and most preferably from about 0.05 mole percent to about 0.35 mole percent.
- mole percent of all monomers in the tagged treatment polymer is calculated based on weight percent.
- the subscripts a, j, t, v, f and c refer to the mole percent of each monomer component of the tagged treatment polymers.
- the remainder of the tagged treatment polymer can have one, two or three additional monomers in it.
- the molecular weights of the instant claimed tagged treatment polymers are from about 500 atomic mass units (hereinafter “a.m.u.”) to about 10,000,000 a.m.u.
- the molecular weights are from about 2000 a.m.u. to about 500,000 a.m.u.
- the molecular weights are from about 5000 a.m.u. to about 40,000 a.m.u.
- Preferred tagged polymers are made via solution polymerization techniques and have a molecular weight from about 5,000 a.m.u. to about 40,000 a.m.u.
- Preferred tagged treatment polymers are where said fluorescent monomer is selected from the group consisting of:
- 5-allyloxy-4′-carboxy-1,8 naphthoylene-1′,2′-benzimidazole (5ACNB) and 6-vinylbenzyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′-benzimidazole (6-VBCNB).
- G is Monomer (Purple) as previously defined;
- Q if present in the polymer, is selected from the group consisting of acrylamide and acrylic acid;
- W if present in the polymer, is selected from the group consisting of acrylamide and acrylamidomethylpropane sulfonic acid;
- S if present in the polymer, is N-sulfomethylacrylamide.
- the most preferred polymers are selected from the group consisting of
- the tagged treatment polymers of the instant claimed invention can be used as scale inhibitors in industrial water systems. As these polymers are consumed performing that function, their fluorescent signal will decrease and thus the decrease in the fluorescent signal can be used to indicate that undesired scaling is taking place.
- the tagged treatment polymers containing a fluorescent monomer can be used in industrial water systems.
- industrial water systems are cooling tower water systems (including open recirculating, closed and once-through systems); petroleum wells, downhole formations, geothermal wells and other oil field applications; boilers and boiler water systems; mineral process waters including mineral washing, flotation and benefaction; paper mill digesters, paper production, washers, bleach plants and white water systems; black liquor evaporators in the pulp industry; gas scrubbers and air washers; continuous casting processes in the metallurgical industry; air conditioning and refrigeration systems; industrial and petroleum process water; indirect contact cooling and heating water, such as pasteurization water; water reclamation and purification systems; membrane filtration water systems; food processing streams (meat, vegetable, sugar beets, sugar cane, grain, poultry, fruit and soybean); and waste treatment systems as well as in clarifiers, liquid-solid applications, municipal sewage treatment and industrial or municipal water systems.
- cooling tower water systems including open recirculating, closed and once-through systems
- the tagged treatment polymer comprising a fluorescent monomer may be used in the industrial water systems singly or in combination with other polymers, which are not tagged.
- the dosage rate of tagged treatment polymer in an industrial water system, when it is being used as a scale inhibitor, is from about 1 to about 100 milligrams of solid component active per liter of water.
- the third aspect of the instant claimed invention is a process for the inhibition of scale formation in an industrial water system which comprises introducing into said industrial water system a tagged treatment polymer, previously described, in an amount sufficient to inhibit scale formation.
- the amount of the tagged treatment polymer comprising the fluorescent monomer added to an industrial water system is in the range of about 1.0 milligrams (mg) to about 30 milligrams of the total solid polymer actives per liter of water in the system. This is equivalent to about 1 part per million (ppm) to about 30 ppm.
- a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
- a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
- An advantage of the fluorescent monomers of this invention is that in their use in the formation of a tagged treatment polymer, the fluorescent monomer is not significantly affected by other structures in the polymer or by other ingredients in the system.
- the polymers are stable in the presence of STA.BR.EX®, where STA.BR,EX® is the trademark for an oxidizing biocide, available from Nalco Chemical Company, One Nalco Center, Naperville, Ill. 60563.
- a further advantage of the tagged treatment polymers of this invention is that the spectral properties, i.e. both excitation and emission of the polymers are in the near visible wavelength region (>370 nm), thus allowing the use of solid state instrumentation and potentially minimize interferences that generally occur in the UV wavelength region.
- Step Two Synthesis of 5-allyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole
- Step Two Synthesis of 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole
- a reactor was charged with deionized water (125 g), and 5-ACNB (prepared according to Monomer Example 1, 0.474 g, 1.16 mmol) and heated to 65° C. with stirring (750 rpm). At temperature, initiator solution 1 (3.50 g ammonium persulfate in 19.59 g of deionized water), and initiator solution 2 (10.48 g sodium metabisulfite in 30.30 g of deionized water) were added separately at a constant flow rate over a period of 3.25 hours.
- initiator solution 1 (2.56 g ammonium persulfate in 30 g of deionized water), initiator solution 2 (7.74 g sodium metabisulfite in 30g of deionized water), and a monomer solution consisting of acrylic acid (88.12 g, 1.22 mole), 49.6% acrylamide (177.56 g, 1.22 mole), 50% sodium hydroxide (36.4 g, 0.455 mole), and 6-VBCNB (prepared according to Monomer Example 2, 0.42 g, 0.943 mmol) were added separately at a constant flow rate over a period of 2 hours. After monomer and initiator feeding was complete, the reaction was held at temperature for an additional 1 hour.
- the product had a molecular weight of approximately 15,000 and 98% incorporation of the tag, as measured by gel permeation chromatography (GPC) calculated from both refractive index and fluorescent detector traces using polystyrene sulfonate (PSS) MW standards.
- GPC gel permeation chromatography
- the oxidizing biocide stability test was performed in the following manner. Solutions of simulated water were prepared with the desired levels of cations and anions at the desired pH. For these experiments the simulated cooling water contained 360 ppm Ca (as CaCO 3 ), 200 ppm Mg (as CaCO 3 ), 300 ppm alkalinity (as CaCO 3 ) and 15 ppm of a stable phosphonate, to stabilize the water and prevent CaCO 3 precipitation. The water was then adjusted to the desired pH with HCl or NaOH. Tests were performed at pH 7 and 9. A series of three amber bottles were labeled with the desired test sample.
- a 25 ml aliquot of the simulated water was delivered into each of the three labeled bottles.
- To one of the bottles (labeled “B”) was delivered 30 ⁇ l of a 1200 ppm stock solution of bleach.
- To a second bottle (labeled “S”) was delivered 30 ⁇ l of a 1200 ppm stock solution of STABREX® biocide, available from Nalco.
- To the third bottle (labeled “N”) was delivered 30 ⁇ l distilled water. The amount of free and total chorine was measured immediately after the samples were prepared and 24 hrs later at the time of fluorescence analysis. The bottles were stored for 24 hrs in the dark. After 24 hours, fluorescence measurements were done using the sample marked “N” as the reference sample.
- % fluorescence consumed (hereinafter “% Fl consumed”) in the presence of an oxidizing biocide was calculated as shown below. It is important to note that lower levels of % Fl Consumed indicate lower loss of fluorescent emission. Results for polymers containing the fluorescent monomers are given in Table I.
- % ⁇ ⁇ F1 ⁇ ⁇ Consumed Intensity ⁇ ⁇ of ⁇ ⁇ N ⁇ ⁇ Sample - Intensity ⁇ ⁇ of ⁇ ⁇ B ⁇ ⁇ or ⁇ ⁇ S ⁇ ⁇ Sample Intensity ⁇ ⁇ of ⁇ ⁇ N ⁇ ⁇ Sample ⁇ 100
- the only decrease or loss of fluorescence signal from the polymer should be due to loss of the polymer under scaling conditions.
- identifying a scaling event as the reason for a loss of fluorescence it is undesirable for the level of fluorescence to also vary based on pH changes, other components present in the cooling water system, or from oxidizing biocides such as the STABREX® biocide system.
- the tagged treatment polymer can be used in an industrial water system. Although a small amount of the tagged treatment polymer is consumed in the presence of 1 ppm STABREX® biocide, the results given above indicate that the tagged treatment polymers are sufficiently stable to be used in industrial water systems where STABREX® is present.
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Abstract
Fluorescent monomers are described and claimed which are synthesized by reacting a substituted or non-substituted naphthalic anhydride with an amine and with a moiety containing a polymerizable group. Such monomers are useful for the preparation of tagged treatment polymers. Such tagged treatment polymers are useful as scale inhibitors in industrial water systems.
Description
This patent application is a continuation-in-part patent application of U.S. patent application Ser. No. 09/560,881 FLUORESCENT MONOMERS AND TAGGED TREATMENT POLYMERS CONTAINING SAME FOR USE IN INDUSTRIAL WATER SYSTEMS, filed Apr. 27, 2000, now U.S. Pat. No. 6,645,881.
This invention relates to fluorescent monomers. In another aspect, this invention relates to tagged treatment polymers that contain these fluorescent monomers. In a further aspect, this invention relates to the use of tagged treatment polymers containing fluorescent monomer(s) therein in industrial water systems.
In many industrial water systems that employ polymers as water treatment agents it may be desirable to tag or mark such polymers to facilitate monitoring thereof. By the term “monitoring” is meant herein any type of tracing or tracking to determine the location or route of the polymers, and any type of determination of the concentration or amount of the polymer at any given site, including singular or intermittent or continuous monitoring. For instance, it may be desirable to monitor water treatment polymers in water systems, or to monitor polymers that may be present in waste fluids before disposal, or to monitor the polymer used in fluids for down-hole oil well applications, or to monitor polymers that may be present in fluids used to wash a manufactured product.
As seen from the above list of possible applications of polymer monitoring, the purpose of such monitoring may be to trace or track or determine the level of the polymer itself, or to trace or track or determine the level of some substance in association with the polymer, or to determine some property of the polymer or substance in association with the polymer, for instance its leachability.
There are many industrial water systems. Because water resources are becoming limited and efficient utilization of water is required, various methods have been adopted to reduce the amount of water used in all industrial water systems. As the methods for reducing the amount of water are put into practice, unfavorable events can occur. These unfavorable events occur because the quality of the water in the system is progressively deteriorated. These unfavorable events can include the formation of scale.
To prevent or minimize unfavorable events, various kinds of treatment agents for treatment of water systems have been used. It has been found that organic substances, including certain types of treatment polymers, are effective for preventing formation of scale. These certain types of treatment polymers are known to persons of ordinary skill in the art of industrial water treatment and are widely used by themselves or as one of many possible components in scale inhibition products.
When a treatment polymer is used for preventing formation of scale the concentration of the treatment polymer in the water system is the important factor so that the treatment polymer performs the desired function with good efficiency. For example, a treatment polymer added to a cooling water system can be consumed by many causes. With consumption, the amount of the treatment polymer dissolved in the cooling water does not remain the same as the amount added to the cooling water. Therefore, it is important for the optimum operation of an industrial water system that practical methods are known to determine the concentration of treatment polymers in the water of the industrial water system.
In general practice, the amount of the treatment polymer added to the water in an industrial water system can be measured using various analytical methods. The use of an inert fluorescent tracer or mass balance measurement method as described in U.S. Pat. Nos. 4,783,314; 4,992,380; and 5,171,450, hereby incorporated by reference; to perform this analysis is known in the art.
In the inert fluorescent tracer method, an inert fluorescent tracer is added to an industrial water system, with the amount of inert fluorescent tracer added being proportional to the amount of the treatment polymer added. By using a fluorometer to measure the fluorescent signal of the inert fluorescent tracer, the amount of the inert fluorescent tracer can be determined by using a calibration curve to relate the amount of fluorescent signal detected to the amount of the inert fluorescent tracer present. Because the inert fluorescent tracer and the treatment polymer are added to the industrial water system in known proportions, by knowing the amount of inert fluorescent tracer present it also means that the amount of treatment polymer present is known.
The inert fluorescent tracer method can be conducted on-line and in real time so that any changes in the amount of treatment polymer being added to the system can be made immediately.
As a complement to the use of an inert tracer system, it has been found that treatment polymers that are used as components of scale inhibitors in industrial water systems could be monitored if tagged with a fluorescent monomer. The amount of fluorescent monomer incorporated into the tagged treatment polymer must be enough so that the fluorescence of the tagged treatment polymer can be adequately measured; however, it must not be so much that the performance of the tagged treatment polymer as a treatment agent for the water is decreased. Because the concentration of the tagged treatment polymer itself can be determined using a fluorometer, it is now possible to measure consumption of the tagged treatment polymer directly. It is important to be able to measure consumption directly because consumption of a treatment polymer usually indicates that a non-desired event, such as scaling, is occurring. Thus, by being able to measure consumption of the tagged treatment polymer, there can be achieved an on-line, real time, in-situ measurement of scaling activity in the cooling system.
Certain tagged treatment polymers are known, see U.S. Pat. No. 5,986,030, and U.S. patent application Ser. No. 09/465,146, filed Dec. 16, 1999, now pending, hereby incorporated by reference. However, there is not an abundance of viable tagged treatment polymers for use as treatment polymers in industrial water systems. Therefore, it is desirable to produce additional tagged treatment polymers that have a fluorescent signal so that a fluorometer can be used to measure the fluorescent signal of the tagged treatment polymer and determine the concentration of tagged treatment polymer currently present in the industrial water system from that information.
It is known that tagging of polymers is difficult to accomplish because of the difficulty in chemically combining fluorescent moieties with non-fluorescent polymers. Therefore, in order to synthesize tagged treatment polymers it is also desirable to produce fluorescent monomers that are readily polymerized to form tagged treatment polymers.
The first aspect of the instant claimed invention is a fluorescent monomer selected from the group consisting of compounds of the formulae:
-
- wherein R3 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; and R4 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; with the proviso that when one of R3 or R4 is sulfonic acid and its salts or carboxylic acid and its salts, the other must be allyloxy or vinylbenzyloxy.
The second aspect of the instant claimed invention is a tagged treatment polymer selected from the group consisting of:
GaQjWt (1)
GaQjWt (1)
-
- wherein G is Monomer (Purple), as previously defined;
- wherein Q is selected from the group consisting of acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid, acrylamidomethylpropane sulfonic acid and salts thereof;
- wherein W is selected from the group consisting of:
acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;
with the proviso that Q and W cannot both be the same;
-
- wherein a is from about 0.001 to about 10.0 mole percent;
- wherein j is from about 0 to about 99.999 mole percent;
- wherein t is from about 0 to about 99.999 mole percent; and
- wherein a+j+t=100;
GaQvWfSc (2) - wherein G is as previously defined;
- wherein Q is as previously defined;
- wherein W is as previously defined, with the proviso that Q and W cannot both be the same;
- wherein S is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide;
- wherein a is from about 0.001 to about 10.00 mole percent;
- wherein v is from about 0 to about 97.999 mole percent;
- wherein f is from about 1 to about 97.999 mole percent;
- wherein c is from about 1 to about 40 mole percent; and
- wherein a+v+f+c=100.
The third aspect of the instant claimed invention is a process for the inhibition of scale formation in an industrial water system which comprises introducing into said industrial water system a tagged treatment polymer selected from the group consisting of:
GaQjWt (1)
GaQjWt (1)
-
- wherein G is Monomer (Purple), as previously defined;
- wherein Q is selected from the group consisting of acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid, acrylamidomethylpropane sulfonic acid and salts thereof;
- wherein W is selected from the group consisting of:
acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;
with the proviso that Q and W cannot both be the same;
-
- wherein a is from about 0.001 to about 10.0 mole percent;
- wherein j is from about 0 to about 99.999 mole percent;
- wherein t is from about 0 to about 99.999 mole percent; and
- wherein a+j+t=100;
GaQvWfSc (1) - wherein G is as previously defined;
- wherein Q is as previously defined;
- wherein W is as previously defined, with the proviso that Q and W cannot both be the same;
- wherein S is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide;
- wherein a is from about 0.001 to about 10.00 mole percent;
- wherein v is from about 0 to about 97.999 mole percent;
- wherein f is from about 1 to about 97.999 mole percent;
- wherein c is from about 1 to about 40 mole percent; and
- wherein a+v+f+c=100.
in an amount sufficient to inhibit scale formation.
The fourth aspect of the instant claimed invention is a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
i) adding to said industrial water system a tagged treatment polymer, selected from the group consisting of:
GaQjWt (1)
GaQjWt (1)
-
- wherein G is Monomer (Purple), as previously defined;
- wherein Q is selected from the group consisting of acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid, acrylamidomethylpropane sulfonic acid and salts thereof;
- wherein W is selected from the group consisting of:
acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;
with the proviso that Q and W cannot both be the same;
-
- wherein a is from about 0.001 to about 10.0 mole percent;
- wherein j is from about 0 to about 99.999 mole percent;
- wherein t is from about 0 to about 99.999 mole percent; and
- wherein a+j+t=100;
GaQvWfSc (2) - wherein G is as previously defined;
- wherein Q is as previously defined;
- wherein W is as previously defined, with the proviso that Q and W cannot both be the same;
- wherein S is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide;
- wherein a is from about 0.001 to about 10.00 mole percent;
- wherein v is from about 0 to about 97.999 mole percent;
- wherein f is from about 1 to about 97.999 mole percent;
- wherein c is from about 1 to about 40 mole percent; and
- wherein a+v+f+c=100.
ii) using a fluorometer to detect the fluorescent signal of said tagged treatment polymer;
iii) converting the fluorescent signal of said tagged treatment polymer to the concentration of said tagged treatment polymer; and
iv) adjusting the concentration of said tagged treatment polymer according to what the desired concentration is for said tagged treatment polymer in said industrial water system.
The fifth aspect of the instant claimed invention is a method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
a) adding an inert tracer and a tagged treatment polymer to the water of an industrial water system, wherein said tagged treatment polymer is selected from the group consisting of:
GaQjWt (1)
GaQjWt (1)
-
- wherein G is Monomer (Purple), as previously defined;
- wherein Q is selected from the group consisting of acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid, acrylamidomethylpropane sulfonic acid and salts thereof;
- wherein W is selected from the group consisting of:
acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;
with the proviso that Q and W cannot both be the same;
-
- wherein a is from about 0.001 to about 10.0 mole percent;
- wherein j is from about 0 to about 99.999 mole percent;
- wherein t is from about 0 to about 99.999 mole percent; and
- wherein a+j+t=100;
GaQvWfSc (1) - wherein G is as previously defined;
- wherein Q is as previously defined;
- wherein W is as previously defined, with the proviso that Q and W cannot both be the same;
- wherein S is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide;
- wherein a is from about 0.001 to about 10.00 mole percent;
- wherein v is from about 0 to about 97.999 mole percent;
- wherein f is from about 1 to about 97.999 mole percent;
- wherein c is from about 1 to about 40 mole percent; and
- wherein a+v+f+c=100.
such that a desired concentration of said tagged treatment polymer is present in said water;
b) using a fluorometer to detect the fluorescent signals of said inert tracer and said tagged treatment polymer;
c) converting the fluorescent signals of said inert tracer and said tagged treatment polymer to the concentration of said inert tracer and said tagged treatment polymer; and
d) adjusting the concentration of said tagged treatment polymer according to what the desired concentration is for said tagged treatment polymer in said industrial water system.
Throughout this patent application the following definitions apply:
“anionic counter ion” refers to an organic or inorganic ion that bears a negative charge to counterbalance the positive charge present on the monomer. Examples include, but are not limited to chloride, sulfate, acetate, methylsulfate, hydroxide and bromide;
“aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon atom;
“substituted aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon of an organic molecule which may bear functional groups such as hydroxyl, carboxyl, etc.;
“1,2-diamino-substituted aromatic compound” refers to aromatic diamines in which the two amino groups are attached to two adjacent carbons of an aromatic compound;
“diamines” refers to an organic molecule which bears two amino groups anywhere in the molecule;
“Aldrich” refers to Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wis. 53201 USA, Telephone Numbers (414) 273-3850 and (800) 558-9160;
“alkyl”, whenever it is used, refers to a fully saturated hydrocarbon moiety with from 1 to 10 carbon atoms;
“dialkylamino” refers to a moiety of the formula R21—N—R22, where R21 and R22 are alkyl;
“alkoxy” refers to a moiety of the formula RO—, where R is alkyl;
“alkylamidoalkyl” refers to a moiety of the formula R—C(O)NH—R1—, where R and R1 are alkyl;
“alkylamino” refers to a moiety of the formula R—NH—, where R is alkyl;
“alkoxylalkyl” refers to a moiety of the formula R—O—R1, where R and R1 are alkyl;
“aryl” refers to a moiety of the formula Ar—, where Ar is an aromatic unit; “carboxylate” refers to a moiety of —C(O)OM, where M is H, Na or another cationic counter ion;
“halogen” refers to a moiety selected from the group consisting of F, Cl, Br, and I;
“hydroxyalkyl” refers to a moiety where an —OH group is attached to an alkyl group;
“Nalco” refers to Ondeo Nalco Company, Ondeo Nalco Center, Naperville, Ill. (630) 305-1000;
“vinyl” refers to a moiety which has a carbon-carbon double bond;
“vinylbenzyl” refers to a moiety of the formula;
“aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon atom;
“substituted aliphatic amine” refers to amines in which the amine group is attached to a saturated carbon of an organic molecule which may bear functional groups such as hydroxyl, carboxyl, etc.;
“1,2-diamino-substituted aromatic compound” refers to aromatic diamines in which the two amino groups are attached to two adjacent carbons of an aromatic compound;
“diamines” refers to an organic molecule which bears two amino groups anywhere in the molecule;
“Aldrich” refers to Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wis. 53201 USA, Telephone Numbers (414) 273-3850 and (800) 558-9160;
“alkyl”, whenever it is used, refers to a fully saturated hydrocarbon moiety with from 1 to 10 carbon atoms;
“dialkylamino” refers to a moiety of the formula R21—N—R22, where R21 and R22 are alkyl;
“alkoxy” refers to a moiety of the formula RO—, where R is alkyl;
“alkylamidoalkyl” refers to a moiety of the formula R—C(O)NH—R1—, where R and R1 are alkyl;
“alkylamino” refers to a moiety of the formula R—NH—, where R is alkyl;
“alkoxylalkyl” refers to a moiety of the formula R—O—R1, where R and R1 are alkyl;
“aryl” refers to a moiety of the formula Ar—, where Ar is an aromatic unit; “carboxylate” refers to a moiety of —C(O)OM, where M is H, Na or another cationic counter ion;
“halogen” refers to a moiety selected from the group consisting of F, Cl, Br, and I;
“hydroxyalkyl” refers to a moiety where an —OH group is attached to an alkyl group;
“Nalco” refers to Ondeo Nalco Company, Ondeo Nalco Center, Naperville, Ill. (630) 305-1000;
“vinyl” refers to a moiety which has a carbon-carbon double bond;
“vinylbenzyl” refers to a moiety of the formula;
and “vinylbenzyloxy” refers to a moiety of the formula:
“Chain Transfer Agent” refers to any molecule, used in free-radical polymerization, which will react with a polymer radical forming a dead polymer and a new radical. Representative Chain Transfer Agents are listed by K. C. Berger and G. Brandrup, “Transfer Constants to Monomer, Polymer, Catalyst, Solvent, and Additive in Free Radical Polymerization,” Section II, pp. 81–151, in “Polymer Handbook,” edited by J. Brandrup and E. H. Immergut, 3d edition, 1989, John Wiley & Sons, New York.
“Cross-Linking Agent” refers to an ethylenically unsaturated monomer either containing at least two sites of ethylenic unsaturation or containing one site of ethylenic unsaturation and one site of a reactive group such as an epoxide or an aldehyde. A Cross-Linking Agent is added to branch or increase the molecular weight of the tagged treatment polymer of this invention. Representative Cross-Linking Agents include N,N-methylenebisacrylamide, N,N-methylenebismethacrylamide, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, N-vinyl acrylamide, divinyl benzene, triallyl ammonium salts, N-methyl allylacrylamide, glycidyl acrylate, acrolein, methylolacrylamide, glyoxal, epichlorohydrin, and the like. The crosslinker is added at from about 0.0001 to about 10, preferably from about 0.0001 to about 0.2 weight percent based on the weight of the polymer;
“Branching Agent” refers to a “Cross-Linking Agent” that is administered at a low level (less than 0.05 weight percent based on the weight of the polymer). It is understood that Branching Agents are added to form “branches” not cross-links; and
“HLB” refers to a hydrophilic-lipophilic balance number.
The present invention is based upon the discovery of a group of fluorescent monomers which are useful in the preparation of tagged treatment polymers containing same, with said tagged treatment polymers in turn being able to provide a means for achieving better monitoring in industrial water systems.
The first aspect of the instant claimed invention is a fluorescent monomer selected from the group consisting of compounds of the formulae:
-
- wherein R3 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; and
- R4 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; with the proviso that when one of R3 or R4 is sulfonic acid and its salts or carboxylic acid and its salts, the other must be allyloxy or vinylbenzyloxy.
- Preferred monomers are selected from the group consisting of
- Monomer (Purple),
- wherein R3 is sulfonic and carboxylic acid; and
- R4 allyloxy and vinylbenzyloxy.
The most preferred monomers are monomers of formula Monomer (Purple) where
-
- R3 is carboxylic acid; and
- R4 is vinylbenzyloxy and allyloxy.
- Acceptable names for the most preferred monomers are:
- 5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole and
- 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.
Monomers of formula (Purple) can be synthesized by using two different synthetic routes. Materials required for these syntheses are commercially available and can be obtained from Aldrich.
The first synthetic route involves initially reacting a sulfonic or carboxylic-substituted naphthalic anhydride with 2,3-diamino-phenol. This compound is then further reacted with an allyl or vinylbenzyl halide to yield Monomer (Purple) where R3 is allyloxy or vinylbenzyloxy and R4 is carboxylic or sulfonic acid.
The second synthetic route involves reacting 4-hydroxy-1,8-naphthalic anhydride with a carboxylic or sulfonic-substituted-diamino aromatic compound. This compound is then further reacted with an allyl or vinylbenzyl halide to yield Monomer (Purple) where R3 is carboxylic or sulfonic acid and R4 is allyloxy or vinylbenzyloxy.
“Tagging” the polymer through the use of the fluorescent monomers of this invention is achieved by synthesizing the polymer in the presence of the fluorescent monomer.
Accordingly, once a monomer of Monomer (Purple) is synthesized, the selected monomer can be used to synthesize tagged treatment polymers of formula:
GaQjWt (1)
GaQjWt (1)
-
- wherein G is Monomer (Purple), as previously defined;
- wherein Q is selected from the group consisting of acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, acrylamide, crotonic acid acrylamidomethylpropane sulfonic acid and salts thereof;
- wherein W is selected from the group consisting of:
acrylic acid and salts thereof, methacrylic acid and salts thereof, itaconic acid and salts thereof, maleic acid and salts thereof, maleic anhydride, crotonic acid and salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternary salts, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl acrylamide methyl sulfate quaternary salts, dimethylaminopropyl methacrylamide methyl sulfate quaternary salts, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts (including, but not limited to, sulfuric acid and hydrochloride acid salts), dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;
with the proviso that Q and W cannot both be the same;
-
- wherein a is from about 0.001 to about 10.0 mole percent;
- wherein j is from about 0 to about 99.999 mole percent;
- wherein t is from about 0 to about 99.999 mole percent; and
- wherein a+j+t=100;
GaQvWfSc (2) - wherein G is as previously defined;
- wherein Q is as previously defined;
- wherein W is as previously defined, with the proviso that Q and W cannot both be the same;
- wherein S is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide;
- wherein a is from about 0.001 to about 10.00 mole percent;
- wherein v is from about 0 to about 97.999 mole percent;
- wherein f is from about 1 to about 97.999 mole percent;
- wherein c is from about 1 to about 40 mole percent; and
- wherein a+v+f+c=100.
These tagged treatment polymers can be synthesized by following the procedure for conventional free radical polymerization in an aqueous medium. They can be made by water-in-oil polymerization methods or dispersion polymerization methods or solution polymerization methods. For those tagged treatment polymers containing a sulfomethylated or sulfoethylated acrylamide, the polymers are first created with an acrylamide moiety, and then the acrylamide groups are sulfomethylated using a suitable “sulfo” reagent such as formaldehyde and sodium metabisulfite.
Procedure for Synthesizing Water-In-Oil Emulsion Polymers
The preparation of high molecular weight water-in-oil emulsion polymers has been described in the following references: U.S. Pat. No. 2,982,749 assigned to The Dow Chemical Company; U.S. Pat. No. 3,284,393 assigned to The Dow Chemical Company; U.S. Pat. No. 3,734,873 assigned to Nalco Chemical Company; “Mechanism, Kinetics and Modeling of the Inverse-Microsuspension Homopolymerization of Acrylamide,” by Hundeler, D., Hamielec, A. and Baade, W., Polymer (1989), 30(1), 127–42; and “Mechanism, Kinetics and Modeling of Inverse-Microsuspension Polymerization: 2. Copolymerization of Acrylamide with Quaternary Ammonium Cationic Monomers,” by D. Hunkeler and A. E. Hamielec; Polymer (1991), 32(14), 2626–40.
A general procedure for the manufacture of water-in-oil emulsion tagged treatment polymers is provided to illustrate the preparation of these tagged treatment polymers using fluorescent monomers. The types and quantities of specific components in the formula (monomers, initiators, Chain Transfer Agents, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
An aqueous phase is prepared by mixing together in water one or more water soluble monomers, and different polymerization additives such as inorganic salts, chelants, pH buffers, Chain Transfer Agents and Branching or Cross-Linking Agents. In order to synthesize the tagged treatment polymers of the instant claimed invention, a monomer of formula Monomer (Purple) is included in the aqueous phase at the desired level.
An organic phase is prepared by mixing together an inert hydrocarbon liquid with one or more oil soluble surfactants. The surfactant mixture should have a low HLB, to ensure the formation of an oil continuous emulsion. Appropriate surfactants for water-in-oil emulsion polymerizations, which are commercially available, are compiled in the North American Edition of McCutcheon's Emulsifiers & Detergents. The oil phase may need to be heated to ensure the formation of a homogeneous oil solution.
The oil phase is charged into a reactor equipped with a mixer, a thermocouple, a nitrogen purge tube, and a condenser. Adding the aqueous phase to the reactor containing the oil phase with vigorous stirring forms an emulsion. The resulting emulsion is heated to the desired temperature, purged with nitrogen, and a free-radical initiator is added. The reaction mixture is stirred for several hours under a nitrogen atmosphere at the desired temperature. Upon completion of the reaction, the water-in-oil emulsion polymer is cooled to room temperature, where any desired post-polymerization additives, such as antioxidants, or a high HLB surfactant (as described in U.S. Pat. No. 3,734,873) may be added.
The resulting emulsion polymer is a free-flowing liquid. An aqueous solution of the water-in-oil emulsion polymer can be generated by adding a desired amount of the emulsion polymer to water with vigorous mixing in the presence of a high-HLB surfactant (as described in U.S. Pat. No. 3,734,873).
Procedure for Synthesizing Dispersion Polymers
The preparation of dispersion polymers has been described in the following references: U.S. Pat. No. 4,929,655, assigned to Hymo Corporation; U.S. Pat. No. 5,006,590, assigned to Hymo Corporation; U.S. Pat. No. 5,597,859, assigned to Nalco Chemical Company; European Patent 657,478; U.S. Pat. No. 5,597,858, assigned to Nalco Chemical Company and European Patent 630,909.
A general procedure for the manufacture of dispersion tagged treatment polymers is provided in the following text in order to illustrate the preparation of dispersion tagged treatment polymers comprising the fluorescent monomers described herein. The types and quantities of specific components in the formula (salts and stabilizer polymers, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
An aqueous solution containing one or more inorganic salts, one or more water-soluble monomers, any polymerization additives such as chelants, pH buffers, Chain Transfer Agents, Branching or Cross-Linking Agents and a water-soluble stabilizer polymer is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen purging tube, and a water condenser. The monomer solution is mixed vigorously, heated to the desired temperature, and then a water-soluble initiator is added. The solution is purged with nitrogen while maintaining temperature and mixing for several hours. After this time, the products are cooled to room temperature, and any post-polymerization additives are charged to the reactor. Water continuous dispersions of water-soluble polymers are free flowing liquids with product viscosities generally 100–10,000 cP, measured at low shear. Thus, in order to prepare tagged polymers as dispersions, a monomer of formula Monomer (Purple) is included in the reaction mixture at the desired level.
Procedure for Synthesizing Solution Polymers
A general procedure for the manufacture of solution polymers is provided to illustrate the preparation of the solution tagged treatment polymers comprising the fluorescent monomers described herein. One typical process is described as follows: One or more monomers are added to a vessel followed by neutralization with a suitable base. The fluorescent monomer can then be added to this monomer solution after neutralization or alternatively, to the reaction vessel. A determined amount of water is then added to the reaction vessel, which is then heated and purged. Polymerization catalysts may also be added to the vessel initially or fed in gradually during the course of the reaction. Water soluble polymerization initiators such as any azo or redox initiator or combination thereof are added along with the monomer solution to the reaction mixture in separate feeds over the same amount of time, usually 2 to 6 hours. The reaction temperature is maintained at about 60–70° C. Additional initiator may be used after addition is complete to reduce residual monomer levels.
The amount of fluorescent monomer that is used should be an amount sufficient to allow the tagged treatment polymer to be detected in the aqueous environment that it is used. The minimum amount of fluorescent moiety that can be used is that amount which gives a signal-to-noise ratio (S/N) of 3 at the desired tagged treatment polymer dosage. The signal-to-noise ratio is that value where the magnitude of the transduced signal (including but not limited to electronic and optical signals) due to the presence of a target analytic in a measurement device is greater than or equal to a level three (3) times the magnitude of a transduced signal where the analyte (species) of interest is not present in the measurement device.
The amount of fluorescent monomer in the tagged treatment polymers is in the range of from about 0.001 mole percent to about 10 mole percent, preferably from about 0.01 mole percent to about 0.4 mole percent, and most preferably from about 0.05 mole percent to about 0.35 mole percent. For purposes of this patent application, mole percent of all monomers in the tagged treatment polymer is calculated based on weight percent. For purposes of this patent application, the subscripts a, j, t, v, f and c refer to the mole percent of each monomer component of the tagged treatment polymers.
The remainder of the tagged treatment polymer can have one, two or three additional monomers in it.
All molecular weights in this patent application are weight average molecular weights measured by gel permeation chromatography (GPC) calculated from both refractive index and fluorescent detector traces using polystyrene sulfonate (PSS) molecular weight standards. Tagged treatment polymers that have a wide range of molecular weights can be prepared by using the procedures described previously by those skilled in the art.
The molecular weights of the instant claimed tagged treatment polymers are from about 500 atomic mass units (hereinafter “a.m.u.”) to about 10,000,000 a.m.u. Preferably the molecular weights are from about 2000 a.m.u. to about 500,000 a.m.u. Most preferably, the molecular weights are from about 5000 a.m.u. to about 40,000 a.m.u.
Preferred tagged polymers are made via solution polymerization techniques and have a molecular weight from about 5,000 a.m.u. to about 40,000 a.m.u.
Preferred tagged treatment polymers are where said fluorescent monomer is selected from the group consisting of:
5-allyloxy-4′-carboxy-1,8 naphthoylene-1′,2′-benzimidazole (5ACNB) and 6-vinylbenzyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′-benzimidazole (6-VBCNB).
The more preferred polymers are where G is Monomer (Purple) as previously defined; Q, if present in the polymer, is selected from the group consisting of acrylamide and acrylic acid;
W, if present in the polymer, is selected from the group consisting of acrylamide and acrylamidomethylpropane sulfonic acid; and
S, if present in the polymer, is N-sulfomethylacrylamide.
The most preferred polymers are selected from the group consisting of
0.04 mole % 5-ACNB, 49.98 mole % acrylic acid, 49.98 mole % acrylamide; and
0.04 mole % 6-VBCNB, 49.98 mole % acrylic acid, 49.98 mole % acrylamide.
Once created the tagged treatment polymers of the instant claimed invention can be used as scale inhibitors in industrial water systems. As these polymers are consumed performing that function, their fluorescent signal will decrease and thus the decrease in the fluorescent signal can be used to indicate that undesired scaling is taking place.
The tagged treatment polymers containing a fluorescent monomer can be used in industrial water systems. Examples of industrial water systems are cooling tower water systems (including open recirculating, closed and once-through systems); petroleum wells, downhole formations, geothermal wells and other oil field applications; boilers and boiler water systems; mineral process waters including mineral washing, flotation and benefaction; paper mill digesters, paper production, washers, bleach plants and white water systems; black liquor evaporators in the pulp industry; gas scrubbers and air washers; continuous casting processes in the metallurgical industry; air conditioning and refrigeration systems; industrial and petroleum process water; indirect contact cooling and heating water, such as pasteurization water; water reclamation and purification systems; membrane filtration water systems; food processing streams (meat, vegetable, sugar beets, sugar cane, grain, poultry, fruit and soybean); and waste treatment systems as well as in clarifiers, liquid-solid applications, municipal sewage treatment and industrial or municipal water systems.
The tagged treatment polymer comprising a fluorescent monomer may be used in the industrial water systems singly or in combination with other polymers, which are not tagged. The dosage rate of tagged treatment polymer in an industrial water system, when it is being used as a scale inhibitor, is from about 1 to about 100 milligrams of solid component active per liter of water.
The third aspect of the instant claimed invention is a process for the inhibition of scale formation in an industrial water system which comprises introducing into said industrial water system a tagged treatment polymer, previously described, in an amount sufficient to inhibit scale formation. The amount of the tagged treatment polymer comprising the fluorescent monomer added to an industrial water system is in the range of about 1.0 milligrams (mg) to about 30 milligrams of the total solid polymer actives per liter of water in the system. This is equivalent to about 1 part per million (ppm) to about 30 ppm.
When used in an industrial water system, the fluorescent signal of the tagged treatment polymers can be used to determine how much tagged treatment polymer is present in the industrial water system. Therefore, the fourth aspect of the instant claimed invention is:
A method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
-
- i) adding to said industrial water system a tagged treatment polymer, wherein said tagged treatment polymer is as previously described;
- ii) using a fluorometer to detect the fluorescent signal of said tagged treatment polymer;
- iii) converting the fluorescent signal of said tagged treatment polymer to the concentration of said tagged treatment polymer; and
- iv) adjusting the concentration of said tagged treatment polymer according to what the desired concentration is for said tagged treatment polymer in said industrial water system.
- The fifth aspect of the instant claimed invention is as follows.
A method for maintaining the desired amount of tagged treatment polymer in an industrial water system comprising the steps of:
-
- a) adding an inert tracer and a tagged treatment polymer, as previously described, to water such that a desired concentration of said tagged treatment polymer is present in said water;
- b) using a fluorometer to detect the fluorescent signals of said inert tracer and said tagged treatment polymer;
- c) converting the fluorescent signals of said inert tracer and said tagged treatment polymer to the concentration of said inert tracer and said tagged treatment polymer; and
- d) adjusting the concentration of said tagged treatment polymer according to what the desired concentration is for said tagged treatment polymer in the industrial water system.
An advantage of the fluorescent monomers of this invention is that in their use in the formation of a tagged treatment polymer, the fluorescent monomer is not significantly affected by other structures in the polymer or by other ingredients in the system. Thus, the polymers are stable in the presence of STA.BR.EX®, where STA.BR,EX® is the trademark for an oxidizing biocide, available from Nalco Chemical Company, One Nalco Center, Naperville, Ill. 60563.
A further advantage of the tagged treatment polymers of this invention is that the spectral properties, i.e. both excitation and emission of the polymers are in the near visible wavelength region (>370 nm), thus allowing the use of solid state instrumentation and potentially minimize interferences that generally occur in the UV wavelength region.
The following examples are presented to be illustrative of the present invention and to teach one of ordinary skill how to make and use the invention. These examples are not intended to limit the invention or its protection in any way.
Step One: Synthesis of 5-chloro-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole(I)
A 100 ml round bottom flask was charged with 4-chloro-1,8-naphthalic anhydride (4.65 g, 19.99 mmol) 3,4-diaminobenzoic acid (3.08 g, 20.24 mmol), and glacial acetic acid (50 ml). The mixture was refluxed under nitrogen for 5 hours and cooled. The solid was collected, washed with isopropanol, and dried under vacuum.
Step Two: Synthesis of 5-allyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole
A 300 ml Parr reactor was charged with 5-chloro-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole(I) (0.7 g, 2.01 mmol), allyl alcohol (20 ml, 0.294 mole), and potassium hydroxide (0.23 g, 4.1 mmol). The reactor was purged for 10 minutes, sealed and then heated to 150° C. for 4 hours. Upon cooling, the volatiles were stripped and a crude orange solid was obtained.
Step One: Synthesis of 6-hydroxy-4′-carboxyl-1,8-naphthoylene-1′,2′-benzimidazole(I)
A 100 ml round bottom flask was charged with 3-hydroxy-1,8-naphthalic anhydride (4.29 g, 20.04 mmol), 3,4-diaminobenzoic acid (3.04 g, 19.97 mmol), and glacial acetic acid (50 ml). The mixture was refluxed under nitrogen for 5 hours and cooled. The solid was collected, washed with isopropanol, and dried under vacuum.
Step Two: Synthesis of 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole
A 100 ml round bottom flask was charged with 6-hydroxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole(I) (1.66 g, 4.5 mmol), vinyl benzyl chloride (0.92 g, 6.05 mmol), and potassium carbonate (2.38 g, 10 mmol). The mixture was refluxed in acetone for 8 hours and cooled. The mixture was then poured into water, acidified, and the orange solid was collected.
A reactor was charged with deionized water (125 g), and 5-ACNB (prepared according to Monomer Example 1, 0.474 g, 1.16 mmol) and heated to 65° C. with stirring (750 rpm). At temperature, initiator solution 1 (3.50 g ammonium persulfate in 19.59 g of deionized water), and initiator solution 2 (10.48 g sodium metabisulfite in 30.30 g of deionized water) were added separately at a constant flow rate over a period of 3.25 hours. Five minutes after initiator feed had started, a monomer solution consisting of deionized water (13.57 g), acrylic acid (95.43 g, 1.33 mole), 48.7% acrylamide (193.23 g, 1.33 mole), and 50% sodium hydroxide (42.3 g, 0.529 mole) was added separately at a constant flow rate over a period of 3 hours. After monomer and initiator feeding was complete, the reaction was held at temperature for an additional 30 minutes. The product had a molecular weight of approximately 11,600 and 92% incorporation of the tag, as measured by gel permeation chromatography (GPC) calculated from both refractive index and fluorescent detector traces using polystyrene sulfonate (PSS) MW standards.
A 5-neck, 1000 ml resin flask equipped with a mechanical stirrer, side baffles, reflux condenser, and nitrogen purge was charged with deionized water (133.96 g) and heated to 65° C. with stirring (800 rpm). At temperature, initiator solution 1 (2.56 g ammonium persulfate in 30 g of deionized water), initiator solution 2 (7.74 g sodium metabisulfite in 30g of deionized water), and a monomer solution consisting of acrylic acid (88.12 g, 1.22 mole), 49.6% acrylamide (177.56 g, 1.22 mole), 50% sodium hydroxide (36.4 g, 0.455 mole), and 6-VBCNB (prepared according to Monomer Example 2, 0.42 g, 0.943 mmol) were added separately at a constant flow rate over a period of 2 hours. After monomer and initiator feeding was complete, the reaction was held at temperature for an additional 1 hour. The product had a molecular weight of approximately 15,000 and 98% incorporation of the tag, as measured by gel permeation chromatography (GPC) calculated from both refractive index and fluorescent detector traces using polystyrene sulfonate (PSS) MW standards.
Stability and Performance Testing
The fluorescence properties (excitation and emission maxima) of polymers prepared using the monomers are given in Table I. Excitation maxima are all greater than 370 nm. The fluorescence of the polymers remained invariant over a pH range of approximately 2–12.
Another important feature of these polymers is the stability of the fluorescence in the presence of oxidizing biocides. The oxidizing biocide stability test was performed in the following manner. Solutions of simulated water were prepared with the desired levels of cations and anions at the desired pH. For these experiments the simulated cooling water contained 360 ppm Ca (as CaCO3), 200 ppm Mg (as CaCO3), 300 ppm alkalinity (as CaCO3) and 15 ppm of a stable phosphonate, to stabilize the water and prevent CaCO3 precipitation. The water was then adjusted to the desired pH with HCl or NaOH. Tests were performed at pH 7 and 9. A series of three amber bottles were labeled with the desired test sample. A 25 ml aliquot of the simulated water was delivered into each of the three labeled bottles. To one of the bottles (labeled “B”) was delivered 30 μl of a 1200 ppm stock solution of bleach. To a second bottle (labeled “S”) was delivered 30 μl of a 1200 ppm stock solution of STABREX® biocide, available from Nalco. To the third bottle (labeled “N”) was delivered 30 μl distilled water. The amount of free and total chorine was measured immediately after the samples were prepared and 24 hrs later at the time of fluorescence analysis. The bottles were stored for 24 hrs in the dark. After 24 hours, fluorescence measurements were done using the sample marked “N” as the reference sample. The % fluorescence consumed (hereinafter “% Fl consumed”) in the presence of an oxidizing biocide was calculated as shown below. It is important to note that lower levels of % Fl Consumed indicate lower loss of fluorescent emission. Results for polymers containing the fluorescent monomers are given in Table I.
| TABLE I |
| Summary of Fluorescence Properties and |
| Oxidizing Biocide Stability of a Polymer |
| Polymer | Monomer | Fluorescence | Oxidizing Biocide Stability |
| Example | Name | Properties | (% Fluorescence Consumed) |
| 1 | 5-ACNB | Ex = 396 nm | STABREX (pH9) = 1% |
| Em = 511 nm | |||
When using the tagged treatment polymer as a compound of a scale-inhibitor product in an industrial water system, the only decrease or loss of fluorescence signal from the polymer should be due to loss of the polymer under scaling conditions. When identifying a scaling event as the reason for a loss of fluorescence, it is undesirable for the level of fluorescence to also vary based on pH changes, other components present in the cooling water system, or from oxidizing biocides such as the STABREX® biocide system.
If the amount consumed by an oxidizing biocide is equal to or less than 10% of the signal, then the tagged treatment polymer can be used in an industrial water system. Although a small amount of the tagged treatment polymer is consumed in the presence of 1 ppm STABREX® biocide, the results given above indicate that the tagged treatment polymers are sufficiently stable to be used in industrial water systems where STABREX® is present.
The specific examples herein disclosed are to be considered as being primarily illustrative. Various changes beyond those described will, no doubt, occur to those skilled in the art; such changes are to be understood as forming a part of this invention insofar as they fall within the spirit and scope of the appended claims.
Claims (3)
1. A fluorescent monomer selected from the group consisting of compounds of the formulae:
wherein R3 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; and
R4 is sulfonic acid and its salts or carboxylic acid and its salts or allyloxy or vinylbenzyloxy; with the proviso that when one of R3 or R4 is sulfonic acid and its salts or carboxylic acid and its salts, the other must be allyloxy or vinylbenzyloxy.
2. A fluorescent monomer of claim 1 , which is Monomer (Purple), wherein said monomer is named:
5-allyloxy-4′-carboxyl-1,8-naphthoylene-1′,2′ benzimidazole.
3. A fluorescent monomer of claim 1 which is 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.
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Also Published As
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| US20040135124A1 (en) | 2004-07-15 |
| EP1282732A4 (en) | 2004-12-22 |
| ATE444344T1 (en) | 2009-10-15 |
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| CA2404311C (en) | 2010-04-20 |
| MXPA02009969A (en) | 2004-08-19 |
| EP1282732B1 (en) | 2009-09-30 |
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| AR029661A1 (en) | 2003-07-10 |
| EP1282732A1 (en) | 2003-02-12 |
| CA2404311A1 (en) | 2001-11-01 |
| ZA200207690B (en) | 2003-09-25 |
| US6645428B1 (en) | 2003-11-11 |
| US7875720B2 (en) | 2011-01-25 |
| US20040135125A1 (en) | 2004-07-15 |
| DE60140048D1 (en) | 2009-11-12 |
| JP2003531283A (en) | 2003-10-21 |
| TW570969B (en) | 2004-01-11 |
| JP4787451B2 (en) | 2011-10-05 |
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